JP2012051972A - New phosphorus atom-containing phenol resin and method for producing the same, curable resin composition and cured product thereof, resin composition for printed wiring board, printed wiring board, resin composition for flexible wiring board, resin composition for semiconductor sealing material, and resin composition for interlayer insulating material for buildup substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new phosphorus atom-containing phenol resin and a curable resin composition, which are excellent in flame retardancy and heat resistance and can achieve an extremely low thermal expansion coefficient.SOLUTION: The new phosphorus atom-containing phenol resin is obtained by polycondensing a phosphorus atom-containing phenolic compound having a structure represented by a formula (wherein the biphenyl skeleton may be substituted by two phenyl groups) or a derivative thereof and a naphthol compound with formaldehyde. An epoxy resin composition using the phenol resin as a curing agent is provided.

Description

  The present invention is a novel phosphorus atom-containing phenol resin that exhibits excellent performance in flame retardancy, heat resistance and low shrinkage, its production method, curable resin composition excellent in flame retardancy, heat resistance and low shrinkage, The cured product, and a resin composition for a printed wiring board using the curable resin composition, a printed wiring board, a resin composition for a flexible wiring board, a resin composition for a semiconductor sealing material, and an interlayer insulation for a build-up board The present invention relates to a resin composition for materials.

  An epoxy resin composition containing an epoxy resin and a curing agent as an essential component is excellent in various physical properties such as high heat resistance and moisture resistance, and is used for electronic components such as semiconductor encapsulants and printed circuit boards, electronic component fields, and conductive pastes. It is widely used in conductive adhesives such as, other adhesives, matrix for composite materials, paints, photoresist materials, developer materials, and the like.

  In recent years, in these various applications, especially in advanced materials, further improvements in performance typified by heat resistance, moisture resistance, and solder resistance have been demanded. In-vehicle electronic devices that require particularly high reliability, in addition to the shift from the cabin to the higher temperature engine room, the reflow processing temperature has increased due to the compatibility with lead-free solder. Therefore, there is a demand for a material that is more excellent in heat resistance than ever.

  On the other hand, when an epoxy resin composition is used as a printed wiring board material, a halogen-based flame retardant such as bromine is blended with an antimony compound in order to impart flame retardancy. However, in recent environmental and safety initiatives, environmentally and flame-resistant flame retardants that do not use halogen-based flame retardants that may cause dioxins and do not use antimony compounds that are suspected of carcinogenicity. There is a strong demand for the development of a conversion method. In the field of printed wiring board materials, the use of halogenated flame retardants is a factor that impairs reliability at high temperatures.

  In response to such required characteristics, as an epoxy resin composition having both flame retardancy and high heat resistance, for example, Patent Document 1 listed below discloses 9,10-dihydro-9- as a curing agent for epoxy resin. Phosphorus atoms obtained by reacting oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”) with formaldehyde or acetone to obtain a hydroxyl group-containing phosphorus compound, which is reacted with a phenol resin. A technique using a phenol resin containing a resin is disclosed. However, such a phosphorus atom-containing phenol resin has a low reactivity between polyfunctional phenol, HCA and aldehydes in the production process, and a reaction product of HCA and aldehydes is an unreacted component in the generated phenol resin. Since it remained, in addition to being inferior in heat-resistant peelability in the cured product, the flame retardancy was not sufficient. In addition, since the hydroxyl group-containing phosphorus compound obtained by reacting HCA with formaldehyde or acetone is inferior in reactivity with the phenol resin, the types of polyfunctional phenol that can be used are limited. The width of the resin design was severely limited.

  Patent Document 2 below discloses a compound obtained by reacting a reaction product of HCA and hydroxybenzaldehyde with phenol as an intermediate phenol compound of a phosphorus atom-containing epoxy resin.

  However, this phenolic compound also has a low degree of freedom in resin design due to insufficient reactivity between the reaction product of HCA and hydroxybenzaldehyde and phenol, and the final melting point of the phenolic compound is 200 ° C or higher. In addition to being difficult to manufacture industrially, the phenolic compound itself is a crystalline substance and is poor in solubility in an organic solvent, so that it is inferior in handling workability.

  In addition, in the following Patent Document 3, flame retardancy is obtained by using a phosphorus-modified epoxy resin obtained by reacting HCA with a phenol novolac type epoxy resin or a cresol novolak type epoxy resin as a main ingredient and blending with a curing agent for epoxy resin. An epoxy resin composition is disclosed. However, since the epoxy resin composition described in Patent Document 3 reacts with an epoxy group that originally becomes a crosslinking point as a means for introducing phosphorus atoms into the epoxy resin structure, a sufficient crosslinking density is obtained. In other words, the glass transition temperature of the cured product was lowered, so that it could not withstand lead-free solder mounting.

  As a means for imparting flame retardancy to the resin component itself as described above, although a technique using HCA as a modifier for a phenol resin or an epoxy resin is known, a reaction product of HCA and an aldehyde or a ketone has a phenol structure. When a phosphorus atom is to be introduced into the phenol structure by reacting with the aromatic nucleus therein, the heat resistance of the cured product of the phosphorus atom-containing phenol resin obtained due to the low reactivity of the reaction product is sufficient. The current situation was not in the standard.

  Also, for example, in the field of printed wiring boards, in the semiconductor mounting system using the flip chip connection method which has been mainly adopted in recent years, solder balls are arranged between the wiring board and the semiconductor, and the whole is heated and melt-bonded. Since this is a so-called reflow semiconductor mounting method, thermal stress of the wiring board during solder reflow tends to cause a large stress on the solder balls connecting the wiring board and the semiconductor, and poor connection of the wiring. It was. Therefore, generally, insulating materials used for printed wiring boards are required to have a low coefficient of thermal expansion. However, the above-described conventional various phosphorus atom-containing phenol resins and phosphorus atom-containing epoxy resins are all cured products. , The coefficient of linear expansion was high, and the thermal expansion property was inferior in a high temperature environment.

Japanese Patent No. 3464783 Japanese Patent No. 3476780 Japanese Patent No. 3613724

  Therefore, the problem to be solved by the present invention is a novel phosphorus atom-containing phenol resin that has excellent flame retardancy and heat resistance in a cured product and has an extremely low thermal expansion coefficient, a curable resin composition containing the same, and its Cured product, method for producing phosphorus atom-containing phenols used therefor, and printed wiring board resin composition, printed wiring board, flexible wiring board resin composition, and semiconductor encapsulation using the curable resin composition It is providing the resin composition for materials, and the resin composition for interlayer insulation materials for buildup boards.

  As a result of intensive investigations to solve the above problems, the present inventors have reacted a phosphorus atom-containing compound typified by the HCA with an aromatic nucleus of a phenol resin having a resin structure obtained by polycondensation of a naphthol compound and formaldehyde. In this case, first, the phosphorus atom-containing compound is reacted with an aromatic aldehyde having an alkoxy group as a substituent on the aromatic nucleus, and then the reaction product is reacted with a polyfunctional phenol having a naphthol structure. In addition, it has been found that the reactivity is drastically improved, and that the heat resistance and the dimensional stability during heat of the finally obtained cured product of phosphorus atom-containing phenols are drastically improved. It came to complete.

That is, the present invention has a resin structure obtained by polycondensation of a naphthol compound and formaldehyde as a main skeleton, and the structural formulas z1 to z4 shown below as substituents on the aromatic nucleus in the resin structure.

（上記構造式ｚ１〜ｚ４中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立的に、水素原子、炭素原子数１〜５のアルキル基、塩素原子、臭素原子、フェニル基、アラルキル基を表し、Ｒ^５は水素原子又は炭素原子数１〜５のアルキル基を表し、Ｒは炭素原子１〜４のアルキル基を表し、ｎは芳香核上の置換基ＯＲの数であり１〜３である。）
で表される部分構造からなる群から選択される構造部位を有する樹脂構造を有することを特徴とする新規リン原子含有フェノール樹脂に関する。

(In the structural formulas z1 to z4, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
The present invention relates to a novel phosphorus atom-containing phenol resin characterized by having a resin structure having a structural portion selected from the group consisting of the partial structures represented by the formula:

  The present invention further comprises reacting an aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus and an organophosphorus compound (a2) having a P—H group or a P—OH group in the molecular structure. Then, the reaction product obtained is reacted with the polycondensate (a3) of the naphthol compound and formaldehyde, which relates to a method for producing phosphorus atom-containing phenols.

  The present invention further includes a curable resin composition containing an epoxy resin curing agent (A) and an epoxy resin (B) as essential components, and the epoxy resin curing agent (A) contains the novel phosphorus atom. The present invention relates to a curable resin composition characterized by using a phenol resin.

  The present invention further relates to a cured product obtained by curing the curable resin composition.

  The present invention further relates to a printed wiring board resin composition comprising the curable resin composition.

  The present invention further relates to a resin composition for a flexible wiring board comprising the curable resin composition.

  The present invention further relates to a printed wiring board obtained by impregnating a glass substrate with the curable resin composition and then curing the glass substrate.

  The present invention further relates to a resin composition for a semiconductor sealing material further containing an inorganic filler in addition to the curable resin composition.

  The present invention further relates to a resin composition for an interlayer insulating material for build-up substrates, comprising the curable resin composition.

  According to the present invention, a curable resin composition that is excellent in flame retardancy and heat resistance in a cured product and can achieve an extremely low linear expansion coefficient, a cured product thereof, and a method for producing phosphorus atom-containing phenols used therein, In addition, a resin composition for a printed wiring board, a printed wiring board, a resin composition for a flexible wiring board, a resin composition for a semiconductor sealing material, and a resin for an interlayer insulating material for a build-up board using the curable resin composition A composition can be provided.

1 is a GPC chart of the naphthol novolac resin (A-1) obtained in Example 1. FIG.

  Hereinafter, the present invention will be described in detail.

The novel phosphorus atom-containing phenol resin of the present invention has a resin structure obtained by polycondensation of a naphthol compound and formaldehyde as a main skeleton, and the following structural formulas z1 to z4 as substituents on an aromatic nucleus in the resin structure.

（上記構造式ｚ１〜ｚ４中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ独立的に、水素原子、炭素原子数１〜５のアルキル基、塩素原子、臭素原子、フェニル基、アラルキル基を表し、Ｒ^５は水素原子又は炭素原子数１〜５のアルキル基を表し、Ｒは炭素原子１〜４のアルキル基を表し、ｎは芳香核上の置換基ＯＲの数であり１〜３である。）
で表される部分構造からなる群から選択される構造部位を有する樹脂構造を有することを特徴とするものである。

(In the structural formulas z1 to z4, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
It has the resin structure which has a structure site | part selected from the group which consists of the partial structure represented by these.

  Here, the resin structure obtained by polycondensation of naphthol compound and formaldehyde constituting the main skeleton of the novel phosphorus atom-containing phenol resin specifically includes α-naphthol, β-naphthol, and a methyl group and an ethyl group. A polycondensate of a naphthol compound such as a compound in which an alkyl group such as a methoxy group is substituted with a nucleus and formaldehyde, specifically, α-naphthol novolak resin, β-naphthol novolak resin, α-naphthol and β-naphthol. Co-condensation type novolak resins of aldehyde and formaldehyde, and various novolak resins having a molecular structure in which an alkyl group such as a methyl group, an ethyl group, or a methoxy group is substituted by a nucleus, a novolak product of 1,6-dihydroxynaphthalene, 2, Examples thereof include a dihydroxy product of 7-dihydroxynaphthalene. The resin structure is preferably in a range where the average number of naphthol nuclei is 3 to 7 from the viewpoint of excellent flame retardancy and adhesion. Here, the average number of nuclei of the naphthol compound is a value derived based on GPC measurement described later.

  More specifically, such a novel phosphorus atom-containing phenol resin has an aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus, and a P—H group or a P—OH group in the molecular structure. And having the resin structure obtained by the production method of the present invention in which the reaction product obtained is reacted with the polycondensate (a3) of the naphthol compound and formaldehyde. It is preferable that the cured product has excellent flame retardancy and heat resistance.

  The aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus used here is, for example, benzaldehyde, o-tolualdehyde, p-tolualdehyde, o-ethylaldehyde, p-ethylaldehyde, p-isopropylbenzaldehyde. , Naphthaldehydes, anthracene aldehydes and the like as aromatic aldehyde substituents include those having an alkoxy group, specifically, the following structural formula (A1-a)

Wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3 .)
Or a compound represented by the following structural formula (A1-b)

Wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3 .)
The compound (a1-2) represented by these is mentioned.

  In the present invention, among these, the compound (A1-a) is particularly preferable because the phosphorus content in one molecule is high, and particularly, n = 1 is preferable.

  In the present invention, since the aromatic aldehyde (a1) has an alkoxy group as a nucleus substituent, the aromatic aldehyde (a1) and an organophosphorus compound (a2) having a P—H group or a P—OH group, The reactivity of the hydroxyl group produced in the reaction product is excellent, and the product reacts with the aromatic nuclei in the polycondensate (a3) of the naphthol compound and formaldehyde even when almost no catalyst is used. The alkoxy group is preferably a methoxy group or an ethoxy group from the standpoint of such features, and the aromatic aldehyde is preferably benzaldehyde or naphthaldehyde.

  Specifically, the organophosphorus compound (a2) having an aromatic aldehyde (a1) and a reactive P—H group or P—OH group in the molecular structure is represented by the following structural formula (A2-a) or structural formula (A2- b)

(In the structural formula (A2-a) or the structural formula (A2-b), Xa is a hydrogen atom or a hydroxyl group, and R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom or a carbon atom. Represents an alkyl group, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl group of formulas 1 to 5.)
The compound represented by these is mentioned. ^Here, as ^{R 1, R 2, R 3} , an alkyl group having 1 to 5 carbon atoms constituting the ^{R 4,} a methyl group, an ethyl group, n- propyl group, i- propyl, t- butyl group, An n-pentyl group may be mentioned.

In the present invention, from the point that the reactivity of the compound (X) produced by the reaction with the aromatic aldehyde (a1), the polycondensate (a3) of naphthol compound and formaldehyde is extremely good, X2 in A2-a) or structural formula (A2-b) is preferably a hydrogen atom, and is represented by the structural formula (A2-a) from the viewpoint of excellent flame retardancy of a cured product of a phosphorus atom-containing phenol. Are preferred. In particular, 9,10-dihydro-9-oxa-10 in which R ¹ , R ² , R ³ and R ⁴ are all hydrogen atoms and Xa is a hydrogen atom in the structural formula (A2-a). -The point that it is the phosphaphenanthrene-10-oxide, and the flame retardance and heat resistance of the cured product of the phosphorus atom-containing phenols finally obtained are excellent. To preferred.

  Here, the reaction conditions of the aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus and the organophosphorus compound (a2) having a P—H group or a P—OH group are, for example, 80 to 180. It can be performed under the temperature condition of ° C. The reaction can be performed without a catalyst, or can be performed in the presence of a non-ketone organic solvent such as an alcohol organic solvent or a hydrocarbon organic solvent.

  The compound (X) produced by this reaction is, for example, a compound represented by the structural formula (a1-1) as the aromatic aldehyde (a1), a structural formula (a2-1) or the organic phosphorus compound (a2), or When the compound represented by the structural formula (a2-2) is used, the following structural formulas x1 to x4

(In the structural formulas x1 to x4, R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
Is mentioned.

  Among these, the compounds represented by the structural formulas x1 and x2 are preferable because they are particularly excellent in reactivity with the naphthol novolak resin component (a3), and the flame retardant of a cured product of phosphorus atom-containing phenols finally obtained is particularly preferable. The compound represented by the structural formula x1 is preferable from the viewpoint of excellent properties.

  Next, the polycondensate (a3) of the naphthol compound and formaldehyde used in the present invention is a compound in which α-naphthol, β-naphthol, and an alkyl group such as a methyl group, an ethyl group, or a methoxy group are substituted by a nucleus. Polycondensates of naphthol compounds such as aldehydes, specifically, α-naphthol novolak resins, β-naphthol novolak resins, α-naphthols and co-condensation type novolak resins of β-naphthols and formaldehyde, and these Examples thereof include various novolak resins having a molecular structure in which an alkyl group such as a methyl group, an ethyl group, or a methoxy group is substituted with a nucleus, a novolak product of 1,6-dihydroxynaphthalene, a dihydroxy product of 2,7-dihydroxynaphthalene, and the like.

  In the present invention, the naphthol novolak resin (a3) is a composition of the naphthol novolak resin (a3) and the naphthol compound (a3-2), and the naphthol compound (a3-2) in the composition Use as a composition (hereinafter, abbreviated as “naphthol novolak resin composition”) in which the content on a peak area basis in GPC measurement is 1 to 6% is particularly used for printed wiring boards. It is preferable in that it has excellent delamination strength and can further improve the flame retardancy.

Here, the content of the naphthol compound (a3-2) in the naphthol novolak resin composition on the basis of the peak area in the GPC measurement is a polycondensate (a3) of the naphthol compound and formaldehyde calculated by the GPC measurement. Is the ratio of the peak area of the naphthol compound (a3-2) to the total peak area of the naphthol novolak resin composition that is a mixture of the naphthol compound (a3-2) and specifically measured by the following method. And a calculated value.
<GPC measurement conditions>
3) GPC: The measurement conditions are as follows.

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.

(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

<Calculation method of content rate>
The calculation method of the content rate on the basis of the peak area of the naphthol compound (a3-2) is the measurement of the naphthol novolak resin composition under the above GPC measurement conditions, and the naphthol compound for all the peak areas of the detected phenol resin composition. It is a value calculated by the ratio of the peak area of (a3-2).

  Here, examples of the naphthol compound (a3-2) include α-naphthol, β-naphthol, and compounds in which an alkyl group such as a methyl group, an ethyl group, or a methoxy group is substituted by a nucleus. In particular, α-naphthol is preferable from the viewpoint of excellent reactivity and remarkable effects of the present invention.

  Further, the polycondensate (a3) of the naphthol compound and formaldehyde is a naphthol novolak resin using the same compound as the naphthol compound (a2) as a raw material. It is preferable from the viewpoint of excellent flammability. Furthermore, the polycondensate (a3) of the naphthol compound and formaldehyde is preferably in a range where the average number of naphthol nuclei is 3 to 7 from the viewpoint of excellent flame retardancy and adhesion. Here, the average number of nuclei of the naphthol compound is a value derived by the GPC measurement described above.

  In the naphthol novolak resin composition described above, a polycondensate (a3) of a naphthol compound and formaldehyde and a naphthol compound (a3-2) are blended so that the area ratio in the latter GPC measurement is 1 to 6%. As described above, it is preferable to use, as the polycondensate (a3), a naphthol novolak resin using the same compound as the naphthol compound (a3-2) as a raw material. In this case, the area ratio in the GPC measurement of the unreacted naphthol compound (a3-2) in the composition is 1 to 6% under the acid catalyst of the naphthol compound (a3-2) and formaldehyde (f). Producing the naphthol novolak resin composition by a reaction method (hereinafter abbreviated as “Method 1”) is excellent in industrial productivity, excellent in uniformity of the mixture, flame retardancy and It is preferable from the point that the adhesive improvement effect becomes more remarkable.

  In such method 1, the reaction ratio between the naphthol compound (a3-2) and formaldehyde (f) is such that the molar ratio [formaldehyde (f) / naphthol compound (a3-2)] is 0.6 to 0.8. It is preferable from the point which is excellent in a flame retardance and adhesiveness.

  Examples of the formaldehyde source of formaldehyde (f) used in the above reaction include formalin, paraformaldehyde, trioxane and the like. Here, it is preferable that formalin is 30-60 mass% formalin from the point of water dilutability and workability | operativity at the time of manufacture.

  Examples of the acid catalyst used in the above reaction include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid etc. are mentioned. The amount used is preferably in the range of 0.1 to 5% by weight with respect to the total weight of the charged raw materials.

  Moreover, it is preferable from the point which is excellent in the reactivity that the reaction temperature in the method 1 is the range of 80-150 degreeC.

  The phenol resin composition containing the polycondensate (a1) and the naphthol compound (a2) thus obtained has a fluidity and a cured product having a softening point in the range of 110 to 150 ° C. It is preferable from the viewpoint of excellent balance with heat resistance.

  The naphthol novolak resin composition containing the polycondensate (a3) of naphthol compound and formaldehyde described above is a phenol novolac or alkylphenol in addition to the polycondensate (a3) of naphthol compound and formaldehyde and naphthol compound (a3-2). It is preferable to contain a novolak component (a3-3) from the viewpoint that flame retardancy and adhesion can be further improved without lowering the heat resistance of the cured product.

  Here, the phenol novolak or alkylphenol novolak component (a3-3) (hereinafter abbreviated as “novolak component (a3-3)”) means the phenol novolak or alkylphenol novolak (n), the phenol novolak or alkylphenol novolak ( n), a polycondensate (a3 ′) of a naphthol compound and formaldehyde, or a mixture thereof. In particular, a mixture in which the novolak (n) and the polycondensate (a3 ′) are united. It is preferable from the point which is excellent in the improvement effect of a flame retardance and adhesiveness.

  Here, the proportion of the novolak component (a3-3) in the naphthol novolak resin composition is such that the novolak component (a3-3) with respect to the total naphthol skeleton in the polycondensate (a1) and the naphthol compound (a2). The ratio of the total phenol skeleton in the naphthol skeleton per mole is such that the phenol skeleton is 0.2 to 0.01 mole, and the effect of improving flame retardancy and adhesion in the cured product is remarkable. It is preferable from the point which becomes.

Here, the mole ratio of the phenol skeleton per mole of the naphthol skeleton is calculated by ¹³ C-NMR measurement, and specifically is a value measured and calculated by the following method.
< ^13C -NMR measurement conditions>
¹³ C-NMR: Measurement conditions are as follows.

Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination)
Solvent: Dimethyl sulfoxide Pulse angle: 45 ° C pulse Sample concentration: 30 wt%
Accumulation count: 10,000 times <Calculation method of the ratio of moles of phenol skeleton per mole of naphthol skeleton>
When the naphthol novolak resin composition is measured under the above-mentioned ¹³ C-NMR measurement conditions, the integrated value (α) of the peak of the carbon atom to which the hydroxyl group detected between 145 ppm and 160 ppm is bonded is detected between 100 ppm and 140 ppm. The relationship of the integrated value (β) of the peak of carbon atoms to which no hydroxyl group is bonded satisfies the following formula (1) and the following formula (2). Here, (X) represents the number of moles of the naphthol skeleton, and (Y) represents the number of moles of the phenol skeleton.

  Therefore, from the above formulas (1) and (2), the mole ratio (Y / X) of the phenol skeleton per mole of naphthol skeleton can be calculated by the following formula (3).

  As a method for blending the naphthol novolak resin composition with the novolak component (a3-3), specifically, when producing the naphthol novolak resin composition, phenol novolak or alkylphenol novolak (n) and naphthol Method of reacting compound (a3-2) and formaldehyde (f) in an acid catalyst so that the area ratio in GPC measurement of unreacted naphthol compound (a3-2) in the composition is 1 to 6%. (Hereinafter, this is abbreviated as “Method 2”.). In the present invention, the method for producing a naphthol novolak resin composition containing the novolak component (a3-3) by the method 2 is excellent in uniformity of the phenol resin composition, and improves the flame retardancy and adhesion. Is preferable from the point that becomes more prominent.

  Here, specific examples of the phenol novolak or alkylphenol novolak (n) used in Method 2 include phenol novolak, cresol novolak, and t-butylphenol novolak. In the present invention, cresol novolac is preferable from the viewpoint of excellent flame retardancy. The phenol novolak or alkylphenol novolak (n) has a softening point in the range of 60 to 120 ° C., and further has an average number of nuclei in the range of 3 to 10 by GPC measurement under the above conditions. In particular, the phenol resin composition obtained is preferable in that the fluidity of the phenol resin composition is kept high and the effect of improving flame retardancy and adhesion is good.

  The amount of phenol novolak or alkylphenol novolak (n) used in Method 2 is preferably 0.5 to 10% by mass in the raw material components. The raw material component described here refers to the total amount of the naphthol compound (a3-2), formaldehyde (f) and phenol novolak or alkylphenol novolak (n). On the other hand, the reaction ratio between the naphthol compound (a3-2) and formaldehyde (f) is the same as in the case of Method 1 in that the molar ratio [formaldehyde (f) / naphthol compound (a3-2)] is 0.6 to 0. Is preferably from the viewpoint of excellent flame retardancy and adhesion.

  The acid catalyst used in Method 2 is the same as in Method 1, such as inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, and trifluoride. Examples thereof include Lewis acids such as boron, anhydrous aluminum chloride, and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by mass relative to the total weight of the raw materials charged.

  The reaction temperature in Method 2 is preferably in the range of 80 to 150 ° C. from the viewpoint of excellent reactivity.

  Thus, it is preferable that the naphthol novolak resin composition manufactured by the method 2 has a softening point in the range of 110 to 150 from the viewpoint of excellent balance between fluidity in the composition and heat resistance in the cured product.

  The reaction between the aromatic aldehyde (a1) and the compound (X), which is a reaction product of the organophosphorus compound (a2) having a P—H group or a P—OH group, with the naphthol novolak resin component (a3) , 140 to 200 ° C. As described above, in the present invention, the reaction between the compound (X) and the naphthol novolak resin component (a3) is extremely reactive and does not require a catalyst, but may be used as appropriate. Examples of catalysts that can be used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Lewis acid etc. are mentioned. The amount used is preferably less than 5.0% by mass with respect to the total weight of the charged raw materials.

  In the present invention, the reaction ratio between the compound (X) and the naphthol novolak resin component (a3) is not particularly limited. Rather, because of its good reactivity, the intended flame retardancy and heat resistance are achieved. The modified amount of the compound (X) with respect to the naphthol novolak resin component (a3) can be arbitrarily controlled according to the performance level or the application. However, the reaction is performed in such a ratio that the compound (X) does not remain in the reaction product, specifically, in a ratio of not more than the equivalent to the reaction point on the aromatic nucleus of the naphthol novolak resin component (a3). It is preferable. Further, when the compound (X) is modified into a novolak type phenol resin or an aralkyl type phenol resin preferably used as the naphthol novolak resin component (a3), the phosphorus atom content is 4.0 to 7.0 on a mass basis. It is preferable from the point which is the range used as the ratio which becomes the mass% from the point which is excellent in heat resistance and a flame retardance.

  After the reaction, the desired product can be obtained by dehydration and drying, if necessary. In the phosphorus atom-containing phenol resin thus obtained, the compound (X) that is an unreacted component hardly remains substantially. For example, when the compound (X) is modified into a novolac-type phenol resin or an aralkyl-type phenol resin and the phosphorus atom content is adjusted to a range of 4.0 to 7.0% by mass, the compound (X ) Is less than the detection limit of GPC in the phosphorus atom-containing phenol resin.

  As described above, the phosphorus atom-containing phenol resin (A) used in the present invention has a molecular structure obtained by the production method described above. The specific molecular structure can be arbitrarily designed by selecting the respective raw material components described above, and the following structural formulas z1 to z4 are used as substituents on the aromatic nucleus of the phenol resin (a3) having a naphthol structure.

(In the structural formulas z1 to z4, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
Those having a molecular structure having a structural portion selected from the group consisting of the partial structures represented by the formula:

  Further, among the partial structures represented by the structural formulas z1 to z4, the partial structure represented by the structural formula z1 or z2 is preferable from the viewpoint of excellent heat resistance of the cured product, and in particular, the structural formula z1. Those represented are preferred.

  Moreover, in this invention, it is preferable from the point of a flame retardance that the phosphorus atom content rate in a novel phosphorus atom containing phenol resin is a ratio used as 4.0-7.0 mass%, In said structural formula z1-z4, The represented partial structure is also preferably present in the phosphorus atom-containing phenols at a ratio satisfying the phosphorus content. The phosphorus atom content is a value calculated by the following formula based on the raw material charge and the raw material outflow during the reaction.

  Next, the curable resin composition of the present invention uses the above-described novel phosphorus atom-containing phenol resin as the epoxy resin curing agent (A), and this and the epoxy resin (B) as essential components. Various epoxy resins can be used as the epoxy resin (B) used here, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; biphenyl type epoxy resin, tetramethylbiphenyl type Biphenyl type epoxy resins such as epoxy resins; phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolak type epoxy resins, epoxidized products of condensates of phenols and aromatic aldehydes having phenolic hydroxyl groups, biphenyl novolak type Novolak type epoxy resins such as epoxy resins; triphenylmethane type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resins; Aralkyl epoxy resin; naphthol novolak epoxy resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy resin, diglycidyloxynaphthalene, 1,1-bis (2, 7-diglycidyloxy-1-naphthyl) epoxy resins having a naphthalene skeleton in the molecular structure such as alkanes; phosphorus atom-containing epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Here, as the phosphorus atom-containing epoxy resin, epoxidized product of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as “HCA”), HCA and quinones Epoxy product of phenol resin obtained by reacting phenolic resin, epoxy resin obtained by modifying phenol novolac type epoxy resin with HCA, epoxy resin obtained by modifying cresol novolac type epoxy resin with HCA, and bisphenol A type epoxy resin using HCA and quinone An epoxy resin obtained by modifying a phenol resin obtained by reacting with a phenol, an epoxy resin obtained by modifying a bisphenol F type epoxy resin with a phenol resin obtained by reacting an HCA and a quinone, and the like Can be mentioned.

  Among the above-mentioned epoxy resins (B), a novolac type epoxy resin and an epoxy resin having a naphthalene skeleton are preferable in the molecular structure from the viewpoint of heat resistance, and a bisphenol type from the viewpoint of adhesion to metals such as copper. Epoxy resins are preferred.

In the curable resin composition of this invention, you may use together the other hardening | curing agent (A ') of the said novel phosphorus atom containing phenol resin as a hardening | curing agent of the said hardening | curing agent for epoxy resins (A). Examples of such other curing agents (A ′) include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyrock resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensation Novolac resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound with phenol nucleus linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound with phenol nucleus linked by bismethylene group) , Aminotriazine-modified phenolic resin (compound having phenol skeleton, triazine ring and primary amino group in the molecular structure) and alkoxy group-containing aromatic ring-modified novolak Examples thereof include polyhydric phenol compounds such as resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferred from the viewpoint of low thermal expansion, and specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls. Resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin, alkoxy group-containing aromatic ring-modified novolak resin (Polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are connected with formaldehyde) is preferable because of its excellent dimensional stability.

  Here, the aforementioned aminotriazine-modified phenol resin, that is, a compound having a phenol skeleton, a triazine ring and a primary amino group in the molecular structure is a molecule obtained by condensation reaction of a triazine compound, a phenol and an aldehyde. What has a structure is preferable from the point which the flame retardance of hardened | cured material becomes favorable. Moreover, in this invention, the thermal expansion coefficient in hardened | cured material is used by using what the nitrogen atom content rate in this compound (A'-b) becomes 10-25 mass%, Preferably it is 15-25 mass%. Is significantly reduced, and excellent dimensional stability can be exhibited.

  Further, when the above-mentioned triazine compound, phenols and aldehydes are subjected to a condensation reaction, in practice, the compound (A′-b) is a mixture of various compounds. Hereinafter, it is preferably used as “mixture (A′-b)”. Furthermore, in the present invention, from the viewpoint of dimensional stability, the nitrogen atom content in the mixture (A′-b) is preferably in the range of 10 to 25% by mass, and more preferably in the range of 15 to 25% by mass.

  Here, the phenol skeleton represents a phenol structure site caused by phenols, and the triazine skeleton represents a triazine structure site caused by a triazine compound.

  The phenols used here are not particularly limited. For example, phenol, o-cresol, m-cresol, p-cresol, xylenol, ethylphenol, butylphenol, nonylphenol, octylphenol and other alkylphenols, bisphenol A Polyphenols such as bisphenol F, bisphenol S, bisphenol AD, tetramethylbisphenol A, resorcin, and catechol, naphthol compounds such as monohydroxynaphthalene and dihydroxynaphthalene, and other phenylphenols and aminophenols. These phenols can be used alone or in combination of two or more. Phenols are preferred because the final cured product is excellent in flame retardancy and excellent in reactivity with amino group-containing triazine compounds.

  Next, the compound containing a triazine ring is not particularly limited, but the following structural formula

(In the formula, R ′ ¹ , R ′ ² and R ′ ³ are any of amino group, alkyl group, phenyl group, hydroxyl group, hydroxylalkyl group, ether group, ester group, acid group, unsaturated group, and cyano group. Represents.)
Or a compound represented by isocyanuric acid is preferred.

Among the compounds represented by the structural formula, melamine and acetoguanamine, in which any two or three of R ′ ¹ , R ′ ² , and R ′ ³ are amino groups are particularly preferred because of their excellent reactivity. An amino group-containing triazine compound represented by a guanamine derivative such as benzoguanamine is preferable.

  These compounds are not limited to one kind in use, and two or more kinds may be used in combination.

  Next, aldehydes are not particularly limited, but formaldehyde is preferable from the viewpoint of easy handling. Although formaldehyde is not limited, Formalin, paraformaldehyde, etc. are mentioned as a typical supply source.

  The blending amount of the epoxy resin (B) and the curing agent for epoxy resin (A) in the curable resin composition of the present invention is not particularly limited, but the obtained cured product has good characteristics. The amount of active hydrogen in the phosphorus atom-containing phenol resin (A) is preferably 0.7 to 1.5 equivalents relative to a total of 1 equivalent of epoxy groups in the epoxy resin (B).

  Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor sealing material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 2-ethyl 4-methyl is used for amine compounds. Imidazole is preferred.

  As described above, the curable resin composition of the present invention described in detail above is characterized by exhibiting excellent solvent solubility. Therefore, the curable resin composition preferably contains an organic solvent (C) in addition to the above components. Examples of the organic solvent (C) that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The proper amount used can be appropriately selected depending on the application, but for example, in a printed wiring board application, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc. The non-volatile content is preferably 40 to 80% by mass. On the other hand, in the adhesive film use for build-up, as the organic solvent (C), for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc. Esters, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and non-volatile content is 30 to 60 mass. It is preferable to use it in the ratio which becomes%.

  The thermosetting resin composition is a non-halogen flame retardant that substantially does not contain a halogen atom in order to exert flame retardancy, for example, in the field of printed wiring boards, as long as the reliability is not lowered. May be blended.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of curable resin composition containing all of halogen-based flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass of red phosphorus is used as a non-halogen flame retardant. It is preferable to mix in the range, and when using an organophosphorus compound, it is preferably mixed in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to do.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, guanylmelamine sulfate, melem sulfate, melam sulfate, etc. Examples thereof include an aminotriazine sulfate compound, aminotriazine-modified phenol resin, and aminotriazine-modified phenol resin further modified with tung oil, isomerized linseed oil, and the like.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The compounding amount of the nitrogen-based flame retardant is appropriately selected according to the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in the range of 1-5 mass parts.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, an epoxy resin, It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of the curing agent, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in 5-15 mass parts.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. In 100 parts by mass of the curable resin composition in which all of epoxy resin, curing agent, non-halogen flame retardant and other fillers and additives are blended, it is preferably blended in the range of 0.005 to 10 parts by mass. .

  An inorganic filler can be mix | blended with the curable resin composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components. The curable resin composition of the present invention in which the epoxy resin of the present invention, a curing agent, and further, if necessary, a curing accelerator are blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications for use of the curable resin composition of the present invention include printed wiring board materials, resin compositions for flexible wiring boards, interlayer insulating materials for build-up boards, semiconductor sealing materials, conductive pastes, and adhesive films for build-ups Resin casting materials, adhesives, and the like. Among these various applications, in printed circuit boards, insulating materials for electronic circuit boards, and adhesive films for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, from the characteristics such as high flame retardancy, high heat resistance, low thermal expansibility, and solvent solubility, it is preferably used for a resin composition for a flexible wiring board, an interlayer insulating material for a build-up board, and a semiconductor sealing material. .

  Here, in order to produce a printed circuit board from the curable resin composition of the present invention, the varnish-like curable resin composition containing the organic solvent (D) is further blended with the organic solvent (D) to obtain a varnish. A method of impregnating a reinforced resin composition into a reinforcing base material and stacking a copper foil to heat-press is mentioned. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. If this method is described in further detail, first, the varnish-like curable resin composition is heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., thereby being a prepreg which is a cured product. Get. The mass ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at a pressure of 1 to 10 MPa at 170 to 250 ° C. for 10 minutes to 3 hours, A desired printed circuit board can be obtained.

  In order to produce a flexible wiring board from the curable resin composition of the present invention, the phosphorus atom-containing phenol resin (A), the epoxy resin (B), the curing accelerator (C), and the organic solvent (D) are added. It mix | blends and it apply | coats to an electrically insulating film using coating machines, such as a reverse roll coater and a comma coater. Subsequently, it heats at 60-170 degreeC for 1 to 15 minutes using a heating machine, volatilizes a solvent, and B-stages an adhesive composition. Next, the metal foil is thermocompression bonded to the adhesive using a heating roll or the like. At that time, the pressure is preferably 2 to 200 N / cm and the pressure is preferably 40 to 200 ° C. If sufficient adhesive performance can be obtained, the process may be completed here. However, when complete curing is required, it is preferably post-cured at 100 to 200 ° C. for 1 to 24 hours. The thickness of the adhesive composition film after finally curing is preferably in the range of 5 to 100 μm.

  In order to prepare a semiconductor sealing material from the curable resin composition of the present invention, in order to prepare an epoxy resin composition prepared for a semiconductor sealing material, the phosphorus atom-containing phenol resin (A), Melt and mix the epoxy resin (B), curing accelerator (C), and compounding agents such as inorganic fillers as necessary using an extruder, kneader, roll, etc. until uniform. Can be obtained. At that time, silica is usually used as the inorganic filler, and the filling rate is preferably in the range of 30 to 95% by mass of the filler per 100 parts by mass of the epoxy resin composition. 70 parts by mass or more is particularly preferable in order to improve the moisture resistance and solder crack resistance and decrease the linear expansion coefficient, and 80 parts by mass or more is more effective in order to significantly increase these effects. Can be increased. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. There is a way to get

  As a method for obtaining an interlayer insulating material for a build-up substrate from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., spray coating method on a wiring board on which a circuit is formed, After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of a curable resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, Lamination is performed on one or both sides of the circuit board by, for example, vacuum laminating so that α) is in direct contact with the circuit board. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  When the curable resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  The method for obtaining the cured product of the present invention may be based on a general curing method for a curable resin composition, but for example, the heating temperature condition may be appropriately selected depending on the kind of curing agent to be combined and the use. However, what is necessary is just to heat the composition obtained by the said method in the temperature range of about room temperature-250 degreeC.

  Therefore, by using the phenol resin, the solvent solubility is dramatically improved compared to the conventional phenol resin modified with phosphorus, and when it is cured, it is excellent in addition to flame retardancy, heat resistance, and heat reliability. Dimensional stability is achieved and it can be applied to the most advanced printed wiring board materials. In addition, the phenol resin can be easily and efficiently produced by the production method of the present invention, and a molecular design corresponding to the target level of performance described above becomes possible.

  Next, the present invention will be specifically described with reference to examples and comparative examples.

Synthesis Example 1 (Synthesis of α-naphthol novolak resin)
A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was charged with 505 parts by mass of α-naphthol (3.50 mol), 158 parts by mass of water, and 5 parts by mass of oxalic acid. The mixture was stirred while raising the temperature in 45 minutes. Subsequently, 177 parts by mass (2.45 mol) of a 42 mass% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, water remaining in the reaction system was removed under reduced pressure by heating to obtain 498 parts by mass of phenol resin (P-1). The softening point of the obtained phenol resin (P-1) was 133 ° C. (B & R method), and the hydroxyl group equivalent was 154 g / eq equivalent.

Synthesis Example 2 (Synthesis of β-naphthol novolak resin)
A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 505 parts by mass of β-naphthol (3.50 mol), 158 parts by mass of water, and 5 parts by mass of oxalic acid. The mixture was stirred while raising the temperature in 45 minutes. Subsequently, 177 parts by mass (2.45 mol) of a 42 mass% formalin aqueous solution was added dropwise over 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C. for 1 hour, and then heated to 180 ° C. in 3 hours. After completion of the reaction, water remaining in the reaction system was removed under reduced pressure by heating to obtain 498 parts by mass of phenol resin (P-2). The obtained phenol resin (P-2) had a softening point of 138 ° C. (B & R method) and a hydroxyl group equivalent of 154 g / eq.

Example 1
Phenol resin (P-1) 308 g (hydroxyl group amount: 2.0 mol), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 129.6 g (0.6 mol), 4-methoxy After charging 81.6 g (0.6 mol) of benzaldehyde and 200 g of 1-methoxy-2-propanol and switching to a vacuum dehydration circuit, the temperature was raised to 180 ° C. and reacted for 8 hours. Next, water was removed under reduced pressure by heating to obtain 508 g of a phosphorus atom-containing naphthol novolak resin (A-1). The resulting phenol resin has a softening point of 155 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) of 300 dPa · s, a hydroxyl group equivalent of 254 g / eq, and a phosphorus content of 3. It was 5 mass%.

Example 2
Phenol resin (P-2) 308 g (hydroxyl group amount: 2.0 mol), 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 129.6 g (0.6 mol), 4-methoxy After charging 81.6 g (0.6 mol) of benzaldehyde and 200 g of 1-methoxy-2-propanol and switching to a vacuum dehydration circuit, the temperature was raised to 180 ° C. and reacted for 8 hours. Subsequently, water was removed under heating and reduced pressure to obtain 508 g of a phosphorus atom-containing naphthalene skeleton-containing phenol resin (A-2). The obtained phenol resin has a softening point of 146 ° C. (B & R method), a melt viscosity (measurement method: ICI viscometer method, measurement temperature: 180 ° C.) of 290 dPa · s, a hydroxyl group equivalent of 254 g / eq, and a phosphorus content of 3. It was 5 mass%.

Comparative Example 1 [Synthesis of Compound described in Patent Document 1 (Patent No. 3647784)]
216 g (1.0 mol) of HCA and 71 g (1.0 mol) of 42 mass% formalin aqueous solution were charged into a reaction vessel, heated to 100 ° C. and reacted for 4 hours. The precipitated solid was then filtered off and washed with acetone to give 2- (6-oxide-6H-dibenz <c, e><1,2> oxa-phosphorin-6-yl) methanol (hereinafter referred to as “ODOPM”). Abbreviated.) 245 g was obtained. The obtained compound had a melting point of 152 to 154 ° C.
An eggplant flask was charged with 144 g of phenol novolac resin (hydroxyl amount: 1.0 mol), and the temperature was raised to 100 ° C. with stirring in a nitrogen stream. After raising the temperature, 230 g (1.0 mol) of ODOPM was added, heated to 140 ° C., and maintained for 12 hours. Subsequently, the mixture was cooled to room temperature, filtered and dried to obtain a phenol resin (A-3).

Comparative Example 2 [Synthesis of Phenol Compound (Phenol Compound (A-4)) described in Patent Document 2 (Patent No. 3476780)]
A flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer is charged with 216 g (1.0 mol) of HCA and 216 g of toluene, heated to 110 ° C. and dissolved by heating. Next, 122 g (1.0 mol) of p-hydroxybenzaldehyde was charged, heated to 180 ° C. and reacted at 180 ° C. for 8 hours, followed by filtration and drying.

で表されるフェノール化合物（Ａ−４）を３３５ｇ得た。得られたフェノール化合物（Ａ−４）の融点は２８６℃であった。

335 g of a phenol compound (A-4) represented by The melting point of the obtained phenol compound (A-4) was 286 ° C.

Comparative Example 3 [Synthesis of phenol resin (A-5)]
In a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube, and a stirrer, 457.6 g (4.4 mol) of phenol novolac resin, 216 g (1.0 mol), and 122 g of p-hydroxybenzaldehyde ( 1.0 mol), the temperature was raised to 180 ° C., and the mixture was reacted at 180 ° C. for 8 hours. Subsequently, water was removed under reduced pressure by heating to obtain 750 g of a phenol resin (A-5). The softening point of the obtained phenol resin is 150 ° C. (B & R method), the melt viscosity (measurement method: ICI viscometer method, measurement temperature: 150 ° C.) is 120 dPa · s, the hydroxyl equivalent is 164 g / eq, and the phosphorus content is 3. It was 7 mass%.

Examples 3 and 4 and Comparative Examples 4 to 7 (Adjustment of epoxy resin composition and evaluation of physical properties)
In accordance with the composition shown in Table 1 below, as the epoxy resin, a phenol novolac type epoxy resin (“N-770” manufactured by DIC, epoxy equivalent: 185 g / eq), a phosphorus atom-containing modified epoxy resin (“FX-” manufactured by Toto Kasei Co., Ltd.) 289ZBEK75 ", epoxy equivalent: 330 g / eq), (A-1) to (A-5) as a curing agent, phenol novolak resin (DIC" TD-2090 ", hydroxyl equivalent 105 g / eq) as main agent: curing agent It mix | blends so that it may become an equivalence ratio 1: 1, Furthermore, 2-ethyl-4-methylimidazole (2E4MZ) is added as a curing catalyst, and the non volatile matter (NV) of each composition will be 58 mass% finally. Thus, methyl ethyl ketone was blended and adjusted.

[Lamination board creation conditions]
Base material: 100 μm Nitto Boseki Co., Ltd. Printed wiring board glass cloth “2116”
Number of plies: 6
Copper foil: 18 μm Nikko Metal Co., Ltd. TCR foil prepreg condition: 160 ° C./2 minutes Curing condition: 200 ° C., 2.9 MPa, 2.0 hours after forming plate thickness: 0.8 mm, resin amount 40%
The following various evaluation was performed using the hardened | cured material created on the said conditions as a test piece. The results are shown in Table 1.

[Heat resistance test and thermal expansion coefficient]
Thermomechanical analysis was performed in a compressed mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.).

Measurement conditions Measurement weight: 88.8mN
Temperature increase rate: 2 times at 3 ° C / minute Measurement temperature range: -50 ° C to 300 ° C
The measurement under the above conditions was performed twice for the same sample, and the average expansion coefficient in the temperature range from 25 ° C. to 280 ° C. in the second measurement was evaluated as the thermal expansion coefficient.

[Burn test] The test method conforms to the UL-94 vertical test.

Abbreviations in Table 1 are as follows.
“A-1”: Phosphorus atom-containing naphthol novolak resin (A-1) obtained in Example 1
“A-2”: Phosphorus atom-containing naphthol novolak resin (A-2) obtained in Example 2
“A-3”: phenolic resin (A-3) obtained in Comparative Example 1
“A-4”: the phenol compound (A-4) obtained in Comparative Example 2
“A-5”: phenolic resin obtained in Comparative Example 3 (A-5)
“TD-2090”: phenol novolac resin (“TD-2090” hydroxyl equivalent: 105 g / eq, manufactured by DIC),
“N-770”: phenol novolac type epoxy resin (“N-770” manufactured by DIC, epoxy equivalent of 185 g / eq),
“FX-289BER75”: Phosphorus-modified epoxy resin (“FX-289BEK75” manufactured by Toto Kasei): obtained by reacting cresol novolac type epoxy resin with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide Epoxy resin, epoxy equivalent 330 g / eq., Phosphorus content 3.0 mass%)

Claims (16)

A resin structure obtained by polycondensation of a naphthol compound and formaldehyde is used as a main skeleton, and the following structural formulas z1 to z4 are used as substituents on the aromatic nucleus in the resin structure.

(In the structural formulas z1 to z4, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
A novel phosphorus atom-containing phenol resin having a resin structure having a structural portion selected from the group consisting of partial structures represented by the formula: An aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus and an organophosphorus compound (a2) having a P—H group or a P—OH group in the molecular structure were reacted, and then obtained. The novel phosphorus atom-containing phenol resin according to claim 1, having a resin structure obtained by reacting the reaction product with a polycondensate (a3) of a naphthol compound and formaldehyde. A naphthol novolak resin composition containing the naphthol compound (a3-2) together with the polycondensate (a3) as a polycondensate (a3) of the naphthol compound and formaldehyde, and the naphthol compound in the composition The novel phosphorus atom containing phenol resin of Claim 1 using the resin mixture which is a ratio from which the content rate on the basis of the peak area in GPC measurement of (a3-2) becomes 1 to 6%. An aromatic aldehyde (a1) having an alkoxy group as a substituent on the aromatic nucleus and an organophosphorus compound (a2) having a P—H group or a P—OH group in the molecular structure were reacted, and then obtained. A method for producing a phosphorus atom-containing phenol, which comprises reacting a reaction product with the polycondensate (a3) of the naphthol compound and formaldehyde. The polycondensate (a3) of the naphthol compound and formaldehyde has the following structural formulas z1 to z4 as substituents on the aromatic nucleus.

(In the structural formulas z1 to z4, R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a chlorine atom, a bromine atom, a phenyl group, or an aralkyl. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R represents an alkyl group having 1 to 4 carbon atoms, n is the number of substituents OR on the aromatic nucleus, and 1 to 3)
The manufacturing method according to claim 4, which has a structural portion selected from the group consisting of partial structures represented by the formula: A naphthol novolak resin composition containing the naphthol compound (a3-2) together with the polycondensate (a3) as a polycondensate (a3) of the naphthol compound and formaldehyde, and the naphthol compound in the composition The manufacturing method of Claim 4 using the resin mixture which is a ratio from which the content rate on the basis of the peak area in GPC measurement of (a3-2) becomes 1 to 6%. It is a curable resin composition which has a hardening | curing agent for epoxy resins (A) and an epoxy resin (B) as an essential component, Comprising: As said hardening | curing agent for epoxy resins (A), any one of the said Claims 1-3 A curable resin composition comprising the novel phosphorus atom-containing phenol resin described in 1. The compounding ratio of the epoxy resin curing agent (A) and the epoxy resin (B) is in the epoxy resin curing agent (A) with respect to a total of 1 equivalent of the epoxy groups of the epoxy resin (B). The curable resin composition according to claim 7, wherein the active hydrogen is in a ratio of 0.7 to 1.5 equivalents. The curable resin composition according to claim 7, further comprising a curing accelerator (C) in addition to the epoxy resin curing agent (A) and the epoxy resin (B). The curable resin composition according to claim 7, further comprising an organic solvent (D) in addition to the components (A) to (C). Hardened | cured material formed by hardening | curing the curable resin composition as described in any one of Claims 7-10. The resin composition for printed wiring boards which consists of a composition of Claim 10. The resin composition for flexible wiring boards which consists of a composition of Claim 10. A printed wiring board obtained by impregnating a glass substrate with the composition according to claim 10 and then curing the glass substrate. The resin composition for semiconductor sealing materials which contains an inorganic filler in addition to the composition of Claim 7. A resin composition for an interlayer insulating material for buildup substrates, comprising the composition according to claim 7.

Images